Performance of Cu-BTC-derived CuOx/C for methanol oxidative carbonylation to dimethyl carbonate
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摘要: 碳基材料负载Cu是一类高效的甲醇氧化羰基化合成碳酸二甲酯催化剂,但存在Cu纳米颗粒易团聚和氧化等问题。采用溶剂热法制备了Cu-BTC,并以其为前驱体,在N2气氛下热解,制备了碳负载Cu及其氧化物(CuOx/C)催化剂。考察了热解温度对Cu纳米颗粒粒径、Cu的价态以及甲醇氧化羰基化合成碳酸二甲酯性能的影响。表征结果显示,升高热解温度有利于Cu2+还原为(Cu0+Cu+),但会导致Cu纳米颗粒团聚。催化剂活性随着热解温度升高而降低,当热解温度为300℃时,制备的CuOx/C-300具有最优的催化活性,碳酸二甲酯的时空收率为1209 mg·g−1·h−1,归因于Cu纳米颗粒的粒径最小(7.5 nm)。经过6次循环实验后,碳酸二甲酯的时空收率降至468 mg·g−1·h−1,催化剂失活的主要原因是(Cu0+Cu+)的氧化和Cu纳米颗粒团聚。Abstract: Carbon-based material supported Cu is an efficient catalyst for methanol oxidative carbonylation to dimethyl carbonate, but Cu nanoparticles are prone to agglomeration and oxidation. Cu-BTC were prepared by hydrothermal method. And then CuOx/C catalysts was prepared by pyrolysis Cu-BTC under N2 atmosphere. The effect of pyrolysis temperature on Cu nanoparticle size, Cu valence state and performance for methanol oxidative carbonylation to dimethyl carbonate were investigated. The characterization results show that increasing the pyrolysis temperature is beneficial to the reduction of Cu2+ to (Cu0+Cu+), but would lead to the agglomeration of Cu nanoparticles. Catalytic activity decreases with the increasing of pyrolysis temperature. CuOx/C-300, prepared by pyrolysis of Cu-BTC at 300℃, shows the optimized catalytic activity and the space-time yield of dimethyl carbonate is 1209 mg·g−1·h−1. This is attributed to the smallest particle size of Cu nanoparticles (7.5 nm). In addition, the space-time yield of dimethyl carbonate decreased to 468 mg·g−1·h−1 after 6 cycle experiments. The main reasons for catalyst inactivation are the oxidation of (Cu0+Cu+) and the agglomeration of Cu nanoparticles.
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Key words:
- catalyst /
- carbon-based materials /
- Cu nanoparticles /
- dimethyl carbonate /
- MOFs /
- pyrolysis /
- oxidative carbonylation
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表 1 催化剂命名和制备条件对照
Table 1. Controls for catalyst nomenclature and preparation conditions
Catalyst Pyrolysis
temperature/℃Heating rate/
(℃·min−1)Pyrolysis
time/hPyrolysis
atmosphereCu-BTC-250 250 5 2 N2 CuOx/C-300 300 5 2 N2 CuOx/C-350 350 5 2 N2 CuOx/C-400 400 5 2 N2 CuOx/C-450 450 5 2 N2 CuOx/C-500 500 5 2 N2 表 2 CuOx/C催化剂中Cu和表面O含量及组成
Table 2. Cu mass fraction and surface O fraction and content of CuOx/C catalysts
Catalyst Cu/wt%① O/at%② Area of O1s/% C=O O=C—O C—OH CuOx/C-300 63.1 26.9 90.9 3.6 5.5 CuOx/C-350 58.2 14.3 71.4 3.6 25.0 CuOx/C-400 61.6 13.6 44.3 6.4 49.3 CuOx/C-450 61.8 11.6 34.9 5.9 59.2 CuOx/C-500 56.6 10.5 39.5 4.0 56.5 Notes: ①—Determined based on ICP-OES results; ②—Determined based on fitting results of XPS survey spectra. 表 3 催化剂性能
Table 3. Catalytic performance of catalysts
Catalyst CMeOH/% SDMC/% STYDMC/(mg·g−1·h−1) Cu-BTC 0 0 0 Cu-BTC-250 0 0 0 CuOx/C-300 2.19 100 1209 CuOx/C-350 2.01 100 1111 CuOx/C-400 1.71 100 948 CuOx/C-450 1.32 100 724 CuOx/C-500 1.14 100 634 Notes: CMeOH—Conversion of methanol; SDMC—Selectivity of DMC; STYDMC—Space-time yield of DMC. -
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